Professional Documents
Culture Documents
CONTENTS
Many engineering applications require the use of physical properties. Some of these properties are
published in the literature yet in many cases these properties have not been measured yet. Although it
may be possible to measure the physical properties of a substance experimentally, these types of
experiments are often tedious and time consuming. Thus in the absence of reliable experimental data
physical properties need to be estimated with sufficient accuracy for the purpose required. The
purpose of this text is not to discuss all property estimation methods in detail but rather to introduce
Various methods are used in development of the estimation correlations. Some are based on theory
with empirical parameters, other totally based on fitting available data while some are based on the
theory of corresponding states. Before we discuss the methods to predict some properties, a short
discussion on some general methods widely used is presented:
Proposed by van der Waals in 1873, the law of corresponding states expresses the generalisation that
equilibrium properties which depend on intermolecular forces are related to the critical properties in a
universal kind of way. The law of corresponding states provides the single most important basis for the
development of correlations and estimation methods. The macroscopic version of the law of
corresponding states is as follows:
All fluids at the same reduced temperature and reduced pressure have the same compressibility
factor.
Consider, for example, a plot of the reduced pressure versus the reduced volume for methane and
nitrogen at saturated conditions and at a reduced temperature of 1.1. (See Figure 1). As seen, the
plots coincide well and illustrate the principle of corresponding states.
10
Reduced Pressure
1 Methane Saturated
Nitrogen Saturated
Methane Tr = 1.1
0.01
0.1 1 10 100 1000
Reduced Volume
The concept of the law of corresponding states is used in the development of compressibility charts
and is the basis for many equations of state. Compressibility charts have been discussed in detail in
Chemical Engineering 254 already and although not being discussed in this course, it should be noted
that compressibility charts are a useful tool in describing PvT behaviour. Successful application of the
principle of corresponding states to PvT data has encouraged similar correlations for other properties
and a number of correlations given here will be based on the law of corresponding states.
Group contribution methods of estimating chemical properties originate from the concept that each
chemical group in a compound contributes to the property in its own unique way. Although not without
flaws, these methods are able to predict some properties with reasonable accuracy. State of the art
group contribution methods, although quite complex, are accurate and reliable enough for most
A number of properties of compounds are fitted to (semi) empirical correlations. Sometimes these
correlations have a theoretical basis with fitted constants (semi-empirical correlations) and sometimes
the correlations are based on the best fit of a mathematical equation with little or no theoretical
foundation (empirical correlations). Care should be taken when applying such correlations: The range
of application is usually given as well as the units. When applied outside the range of application,
incorrect / inaccurate results may be obtained. However, within the range of application, (semi)
empirical correlations often provide a good method for estimating the properties of an equation.
With regard to critical constants, a number of terms need to be defined as they are used extensively in
predicting properties of substances.
Critical point: The critical point is the point (pressure, temperature, specific volume and
compressibility) on the vapour pressure curve at which two co-existing
phases become identical. This point is unique for every pure component.
Critical temperature(Tc): The critical temperature is the temperature at the critical point. This is the
temperature above which a gas can not be condensed by increasing the
temperature, i.e. the temperature above which the liquid phase can not
be formed irrespective of the pressure of the system. The critical
temperature is important in determining the phase boundaries of
compounds and is often a parameter in, amongst others, equations of
state and in vapour pressure correlations.
Reduced temperature (Tr): The reduced temperature is the dimensionless ratio of the temperature to
the critical temperature (both in absolute values), i.e. Tr = T / Tc.
Critical pressure (Pc): The critical pressure is the pressure at the critical point. This is the
pressure above which a gas can not be condensed by decreasing the
temperature. As is the case for the critical temperature, the critical
pressure is often used as parameter in equations of state and in vapour
pressure correlations.
Reduced pressure (Pr): The reduced pressure is the dimensionless ratio of the absolute pressure
to the critical pressure, i.e. Pr = P / Pc.
Critical volume (vc): The critical volume is the specific volume at the critical point, i.e. the
volume occupied by the compound at the critical temperature and
pressure. The critical volume is sometimes used in equations of state as
well as in estimating the volumetric fractions.
Critical compressibility (Zc) The critical compressibility is the compressibility at the critical point
calculated from the critical temperature, pressure and volume. The value
is useful and often used in equations of state. (For methods estimating
the critical compressibility please consult general references).
There are a number of literature sources for the critical constants. Some of them include (On reserve
in the library):
th
Perrys Chemical Engineers Handbook, 7 Edition Chapter 2
Many chemical thermodynamics textbooks, including the one prescribed for this course, also list some
critical parameters.
Critical temperature
The critical temperature is usually estimated using the normal boiling temperature. Generally the ratio
between the critical temperature and normal boiling temperature is between 1.5 and 1.8. Guldbergs
rule states:
Guldberg
Tc = 1.5 Tb (1)
Tb = 434.3 K
Therefore Tc = 1.5 * 434.3 K = 651 K
The published experimental value is 625 K (Reid and Prausnitz).
The error is thus 4 %.
Prudhomm found that the sum of the normal melting temperature and normal boiling temperature is
approximately equal to the critical temperature and proposed the following rule:
Prudhomm
Tc = Tb + Tm (2)
Example: Estimate the critical temperature of water and ammonia using Prudhomms Rule:
Water:
Tb = 373.15 K, Tm = 273.15 K
Tc = 373.15 + 273.15 = 646.3 K
The published experimental value is 647.3 K (Koretsky).
The error is thus less than 0.2 %.
Ammonia:
Tb = 239.8 K, Tm = 195.4 K
Tc = 239.8 + 195.4 = 435.2 K
The published experimental value is 405.5 K (Reid and Prausnitz).
The error is therefore greater than 7 %.
The above methods are rough and, as seen, are often not accurate enough. More accurate additive or
group contribution methods can be used. One such method is that of Lydersen. This method of
estimating the critical temperature of hydrocarbon and non-hydrocarbon organic compounds uses a
combination of the normal boiling temperature and the molecular structure to estimate the critical
temperature:
Lydersen
Tb
Tc = (3)
0.567 +
T ( T )2
T is the contribution of each functional group to the critical temperature. The values of T for each
group is given in Table 1 in section 9.1
OH
Tb = 434.3 K
T = 5 * (-CH2- cyclic) + ( C /\ cyclic) + (-OH alcohol)
= 5 * 0.013 + 0.012 + 0.082
= 0.159
From equation 3:
434 .3
Tc =
[
0.567 + 0.159 .0159 2 ]
= 620K
Constantinou and Gani proposed a group contribution method that takes into account both the
structural groups (first order) as well as structural isomerisation (second order). As the second order
contributions are quite complicated, only the first order contributions will be discussed here (For more
accurate predictions, the second order contributions can be considered consult the original article
[1]). The critical temperature can be calculated as follows:
Where n is the number of functional groups (i) present and Tci the contribution of group (i) present. The
values of Tci are given in Table 2 in section 9.2.
Example: Estimate the critical temperature of cyclohexane using the method of Constantiou and Gani
Critical pressure
The critical pressure of organics can be estimated according to the method of Lydersen:
Lydersen:
101325MW
Pc = (Pa ) (5)
(0.34 + p )2
p it the contribution of the functional group to the critical pressure and MW is the molar weight in
g/mol. The values of p for each group is given in Table 1 in section 9.1.
M = 137.38 g/mol
P = (Fluoro) + 3 * (Chloro) + (Quatro subst. Carbon)
= 0.224 + 3 * 0.320 + 0.210 = 1.394
From equation 5:
101325 137 .38
Pc = = 4.63 MPa
(0.34 + 1.394 )2
The published experimental value is 4.41 MPa (Reid and Prausnitz).
The error is thus 5 %
Constantinou and Gani proposed a method to estimate the critical pressure, similar to their method of
estimating the critical temperature:
Pci is the contribution of the functional group (i) to the critical pressure and n is the number of groups
(i) present. The values of Pci are given in Table 2 in section 9.2.
Example: Estimate the critical pressure of n-butanol according to the method of Constantinou and
Gani
The method of Constantinou and Gani, as used, only takes first order interactions into account.
Greater accuracy can be obtained if second order interactions are taken into account, yet, as
previously mentioned, this is beyond the scope of this course.
Critical volume
Methods to calculate the critical volume are similar to those calculating the critical pressure and
temperature. Fedors proposed a method for pure organic compounds:
Fedors
m3
v c = 0.0266 + v
kmol
(7)
v is the contribution of the functional group to the critical volume. The values if v is given in Table 4
in section 9.1
Other methods, similar to those shown for the critical temperature and pressure also exist and have
similar accuracy.
The critical properties of mixtures are often calculated as the molar average value of the individual
values. For example, the critical temperature of a mixture can be calculated as follows:
Please note that x is the MOLE fraction and Tc(n) is the critical temperature of pure compound n.
The boiling point is defined as the temperature at which the vapour pressure of the liquid is equal to
the pressure of one atmosphere on the liquid i.e. the temperature at which the vapour pressure is
101325 Pa. However, if two values of vapour pressure close to 1 atm are available, the normal boiling
point can be interpolated or extrapolated. This is discussed in more detail in the section on vapour
pressures.
The normal boiling point is often published together with critical constants. Good sources for the
normal boiling point include:
th
Perrys Chemical Engineers Handbook, 7 Ed. Chapter 2
th
Properties of Gases and Liquids 4 Ed., Appendix A (p 568 et seq.)
CRC Handbook of Physics and Chemistry, Chapter 3 and Chapter 6
In addition, some suppliers of fine chemicals, such as Sigma-Aldrich, often give the melting points of
their compounds in their catalogues. Caution should be exercised when using values from older
sources since the temperatures were often reported at prevailing conditions (0.95 0.97 atm).
The normal boiling point can also be determined from the vapour pressure curve by setting the
pressure equal to 101325 Pa and solving the temperature. The vapour pressure curve is discussed in
section 3.
Steil and Thodos proposed a method to calculate the boiling points of normal hydrocarbons:
Example: Normal boiling point of decane (10 carbon atoms) according to the method of Steil and
Thodos
1163
Tb = 1209 = 446K
(
1 + 0.0742 10 0.85 )
The experimental value is 447.3 K (Reid and Prausnitz).
The error is thus less than 0.5 %.
The accuracy of correlations such as those of Steil and Thodos are quite good but, as is the case with
the correlation of Steil and Thodos, these types of correlations are often limited to a few compounds.
A number of group contribution methods exist to predict the normal boiling point. Constantinou and
Gani also proposed such a group contribution method, this method being very similar to the ones for
estimating the critical temperature and the critical pressure. The normal boiling point can be estimated
as follows:
Where Tbi is the contribution of the functional group (i) and n the number of groups (i) present. The
values of Tbi are given in Table 2 in section 9.2.
Example: Estimate the normal boiling point of octanoic acid according to the method of Constantinou
and Gani
The acentric factor () is a measure of the shape of a molecule, though it also measures its polarity.
The acentric factor is often used as a parameter in equations of state, hence its importance in
thermodynamics and chemical engineering. By definition, the acentric factor is calculated from the
reduced pressure at a reduced temperature of 0.7:
Critical pressures and temperatures are estimated according to the aforementioned methods. The
vapour pressure can be predicted according to the methods set out below or obtained experimentally.
For small, spherical molecules the acentric factor is essentially zero and it increases as branching,
molecular weight and polarity increases. For mixtures, the acentric factor is usually taken as the
simple molar average value of the compounds in the mixture:
n
= x i i (12)
i=1
Example: Calculate the acentric factor of the LPG mixture given above
The acentric factor is usually published together with the critical constants of a compound.
The vapour pressure at a set temperature is the pressure exerted by a pure component at equilibrium
at this temperature when both liquid and vapour phases exist. The vapour pressure is a continuous
function of temperature and the vapour pressure curve extends from the triple point to the critical
point.
Vapour pressures have been measured extensively, usually as part of thermophysical data of a
compound. Perrys Chemical Engineers Handbook contains a large amount of the thermophysical
data. Another useful source of vapour pressure data is the NIST website. (See section 6).
sat
If the natural logarithm of the vapour pressure (ln(P )) is plotted as a function of the reciprocal of
temperature (1/T) the relationship is often linear over a limited temperature range. This is shown in
Figure 2.
2
ln(Psat) (ln(bar))
0 Ethane
-2 Hexane
Methane
-4
Nitrogen
-6
Water
-8
-10
-12
0.000 0.004 0.008 0.012 0.016
1/T (1/K)
sat
Figure 2: Relationship between 1/T and ln(P ) for ethane, hexane, methane, nitrogen and water
(Data from NIST Website)
sat
If a linear relationship between ln(P ) and 1/T is assumed, the vapour pressure curve can be
expressed as follows:
( )
ln P sat = m
1
T
+c (13)
This is probably the simplest method for predicting the vapour pressure or for interpolating (and to a
limited extent extrapolating) values. If two values on the vapour pressure curve are know, this method
can be used. Referring to equation 13:
m=
( ) ( )
ln P1sat ln P2sat
(14)
1 1
T1 T2
( )
c = ln P1sat m
1
T1
(15)
Using equations 14 and 15, equation 13 can now be used to determine the vapour pressure.
sat
Given: Tb = 231.03 K, P (300.00 K) = 9.9780 bar
( )
At normal boiling point (Conditions 1): ln P1sat = 11.526 and 1/T1 = 0.004328
At 300.1 K (Conditions 2): ( ) = 13.813 and 1/T
ln P2sat 2 = 0.003333
11.526 13.813
m= = 2298
0.004328 0.003333
c = 11.526 ( 2298 ) 0.004328 = 21.474
( )
Therefore: ln P sat = 2298
1
T
+ 21.474 , T in K, P in Pa
o
At 0 C, i.e. 273.15 K:
( )
ln P sat = 2298
1
273.15
+ 21.474 = 13.06
sat
P = 469863 Pa = 4.70 bar.
The NIST website gives the value as 4.75 bar.
The error is thus less than 1.3 %
The Antoine equation is based on the same concept, yet due to the introduction of an additional
parameter is more accurate:
Antoine
( )
ln P sat = A +
B
T+C
(16)
A, B and C are regression constants and are unique to each compound. Table 5 in section 9.4 lists the
parameters for some compounds.
o
Example: Estimate the vapour pressure of carbon tetrachloride at 37 C using the Antoine equation
However, the Antoine equation does not fit the data accurately much above the normal boiling point.
More accurate regression equations are required. These functions usually express the natural
logarithm of the vapour pressure as a function of temperature. Different sources use different
equations. Reid and Prausnitz use three correlations to estimate vapour pressure data for more than
500 compounds. The vapour pressure of these compounds can be expressed by one of three
equations:
( )
ln P sat = A
B
T
+ C ln(T ) +
D P sat
T2
(19)
( )
ln P sat = A
B
T+C
(20)
The values of A, B and C are given in Properties of Gases and Liquids by Reid and Prausnitz (On
sat
reserve in the Library). The correlations use T in K and P in bar.
Equation 3 (equation 20) is in essence the Antoine equation. (See above for example). In equation 1
the pressure is calculated explicitly as a complex function of temperature. On the other hand, equation
2 needs to be solved iteratively. Examples of both equations 1 and 2 follow:
Example: Plot the vapour pressure curve from 260 to 430 K for 2,2-Dimethyl-propane using the
correlation in Reid and Prausnitz
2.5
2
1.5
1
0.5
0
-0.5
-1
0.002 0.0025 0.003 0.0035 0.004
1/T with T in K
As seen, the data generated with the correlation by Reid and Prausnitz
agrees very well with the data on the NIST website
Correlation 2:
A = 42.089, B = 4464.14, C = -4.753, D = 2138 (P in bar, T in K)
Tc = 471.2 K, Pc = 44.1 bar
For 400 K:
P guess LHS RHS Ratio Change
20 2.9957 2.7185 1.1020 Increase Guess
25 3.2189 2.7853 1.1557 Decrease Guess
15 2.7081 2.6517 1.0213 Decrease Guess
14 2.6391 2.6383 1.0003 Decrease Guess
13.9 2.6319 2.6370 0.9981 Increase Guess
13.95 2.6355 2.6376 0.9992 Increase Guess
13.98 2.6376 2.6380 0.9998 Increase Guess
13.99 2.6383 2.6382 1.0001 Close enough
The NIST website gives the value as 14.074 bar.
The accuracy is thus 0.6 %.
Perry
( )
ln P sat = C1 +
C2
T
+ C 3 ln(T ) + C 4 T C5 (21)
th
The values of C1, C2, C3, C4 and C5 are given by Perry (page 2-50 2-54 in Table 2-6, 7 Edition).
The correlations use T in K and P in Pa.
Example: Plot the vapour pressure curve of hydrogen sulphide between 200 and 350 K using the
correlation in Perry
16 Perry
NIST
15
ln(Psat) (Psat in Pa)
14
13
12
11
10
0.0025 0.003 0.0035 0.004 0.0045 0.005
1/T (T in K)
As seen, the data generated with the correlation by Perry agrees very well
with the data on the NIST website
The above methods all estimate the vapour pressure by correlating experimental values and fitting
them to a mathematical expression. Lee and Kesler proposed a method to estimate the vapour
(
ln Prsat = ln Prsat )( ) + (lnP )( )
0
r
sat 1
(22)
Where
This method can be applied at reduced temperatures above 0.3 or above the melting point, whichever
is higher and below the critical point and is most reliable between reduced temperatures of 0.5 and
0.95.
o
Example: Estimate the vapour pressure of 1-butene at 98 C
o
Pure component parameters: Tc = 146.4 C, Pc = 4.02 MPa, = 0.1867
Tr =
(98 + 273.1) = 371.1 = 0.885
(146.4 + 273.1) 419.5
From equation 23:
(
ln Prsat) (0 )
= 5.92714
6.09648
0.885
1.28862 ln 0.885 + 0.169347 0.885 6
= 0.7227
From equation 24:
(
ln Prsat) (1)
= 15.2518
15.6875
0.885
13.4721 ln 0.885 + 0.43577 0.885 6
= 0.6190
From equation 22:
ln Prsat = 0.7227 + 0.1867 ( 0.6190 ) = 0.8383
Prsat = 0.4325
P sat = Prsat Pc
= 0.4325 4.02 = 1.74 MPa
Perry gives an experimental value of 1.72 MPa.
The error is thus 1.2 %
4 THERMAL PROPERTIES
Heat capacity is defined as the amount of energy required to change the temperature of a unit of mass
or mole by one degree. Typical units include J/mol.K and J/kg.K. Heat capacity is usually given either
at constant pressure (Cp) or at constant volume (Cv). Although heat capacity at constant volume is
sometimes used, most engineering applications use heat capacity at constant pressure and we will
thus focus on heat capacity at constant pressure.
In thermodynamics and in heat transfer the heat capacity is often used as a function of temperature in
the definition of enthalpy:
dh = Cp dT (25)
A number of literature sources publish correlations which can be used to determine the heat capacity.
These sources include but are not limited to:
th
Perrys Chemical Engineers Handbook, 7 Edition, Chapter 2
th
Properties of Gases and Liquids 4 Edition, Appendix A
th
Basic Principles and Calculations in Chemical Engineering, 6 Edition
JANNAF Tables
When using such correlations, one needs to take note of the phase that the correlation refers to as
well as the temperature limits of the correlation.
There are also a number of sources that publish values of the heat capacity and / or enthalpy at
specific temperatures and pressures. The sources include but are not limited to:
Steam Tables
th
Perrys Chemical Engineers Handbook, 7 Edition, Chapter 2
This section focuses on energy changes without phase changes. For the energy associated with
phase changes, please see section 4.2.
Harrison and Seaton proposed a method, valid from 300 to 1500 K, to calculate the heat capacity of
an ideal gas based in the type and number of atoms in the molecule:
Where a1 to a15 are constant parameters (See section 1.1 in Table 6) and ni are the number of atoms
of type i.
Example: Estimate the ideal gas heat capacity of acetone (C3H6O) at 600 K
C ig
p =-4.61 + 17.5 * 3 + 10.5 * 6 + 17.5 * 1 = 128 J/mol.K
Daubert et al. reported the experimental value as 121.8 J/mol.K.
The error is thus 5.5 %
However, the method of Harrison and Seaton is limited to ideal gases and does not provide the heat
capacity as an explicit function of temperature. Rihani and Doraiswamy suggested a group
contribution method to determine the heat capacity of vapours as a function of temperature. The heat
capacity has the following temperature functionality:
C p = a + bT + cT 2 + dT 3 (27)
a = n ai (28)
b = n bi (29)
c = n ci (30)
d = n di (31)
Example: The vapour heat capacity of 3-methyl-1,2-butaniene as a function of temperature and at 300
K according to the method of Rihani and Doraiswamy
CH3
H2C C C
Therefore
a = 2 * 0.6087 + 2.6308 = 3.8483
b = 2 * 2.1433E-2 + 4.1658E-2 = 8.4524E-2
c = 2 * (-0.0852)E-4 + (-0.2845)E-4 = -0.4549E-4
d = 2 * 0.001135E-6 + 0.007277E-6 = 0.009547E-6
Shaw proposed a group contribution method to estimate the liquid heat capacity at constant pressure
o
at 25 C:
Shaw
C p = nC pi (32)
Where Cpi is the contribution of functional group (i) and n the number of groups (i) present. The values
of Cpi are given in Table 13 in section 9.7.
Example: Estimate the heat capacity of hexane and heptane at 298.15 K using the method of Shaw
Hexane:
Two CH3 groups, i.e. 8.80 * 2 = 17.60
Four CH2 groups, i.e. 7.26 * 4 = 29.04
Cp = 17.60 + 29.04 = 46.6 cal/mol.K
This NIST website gives the value as 46.379 cal/mol.K
The error is thus 0.5 %
Heptane:
Two CH3 groups, i.e. 8.80 * 2 = 17.60
Four CH2 groups, i.e. 7.26 * 5 = 36.30
Cp = 17.60 + 36.30 = 53.9 cal/mol.K
This NIST website gives the value as 53.657 cal/mol.K
The error is thus 0.5 %
o
The method of Shaw, although simple and quite accurate is limited to 25 C. Rika and Domalski
proposed a group contribution method that is able to express the heat capacity of liquids as a second
order polynomial function of temperature. The method is applicable between the melting temperature
a = n ai (34)
b = n bi (35)
d = n di (36)
The temperature is in K and the unit of Cp then depends in the unit of R. The values of ai, bi and di for
linear aliphatic and aromatics hydrocarbons are given in Table 14 in section 9.8. Parameters for
halogen, nitrogen, oxygen and sulphur groups are given in Table 15 in section 9.8. The method can be
extended to include second order interactions. This is beyond the scope of this course. (If required,
please consult the original texts [2,3].)
Example: Determine a temperature dependent correlation for the heat capacity of hexane and
estimate the heat capacity at 298.15 K
At 298.15 K:
= 195.1 J
mol.K
The NIST website gives a value of 194.0 J/mol.K
The error is thus 0.5 %
As a first approximation the heat capacity of mixtures can be approximated by calculating the molar
average of the constituent compounds:
n
Cp (T ) = x iCpi (T ) (37)
i=1
When a substance changes phase, the enthalpy of the substance changes. This section concerns
itself with the energy associated with phase changes.
The enthalpy of vapourisation (hvap) is defined as the difference in the enthalpies of a unit of mole or
mass of a saturated vapour and a saturated liquid of a pure component. Basically, the enthalpy of
vapourisation is the energy required to vapourise a unit of mole or mass at the said temperature.
Similarly, the enthalpy of vapourisation is the amount of energy released when a unit mole or mass is
condensed at the said temperature.
Enthalpies of vapourisation are often published together with saturated enthalpies in sources such as
the steam tables and Perry.
Pitzer et al. proposed a method based in the corresponding states approach that only requires the
critical temperature and acentric factor:
Pitzer et al.
h vap
= 7.08(1 Tr ) + 10.95 (1 Tr )
0.354 0.456
(38)
RTc
Example: Estimate the enthalpy of vapourisation for propionaldehyde at 350 K using the method of
Pitzer et al.
Riedel proposed a method of estimating the enthalpy of vapourisation at the normal boiling point:
Reidel
Pc
ln 1
Tb 101.325
h vap, b = 1.039 R Tc (39)
Tc T
0.930 b
Tc
In equation 39, the critical pressure is in kPa and the critical temperature in K.
Constantinou and Gani proposed a group contribution method to calculate the enthalpy of
vapourisation at 298 K:
Where n is the number of functional groups (i) present and hvi the contribution of groups (i) present.
The values of hvi are given in 9.2 in Table 3.
Example: Estimate the enthalpy of vapourisation of methanol at 298 K according to the method of
Constantinou and Gani
The enthalpy of vapourisation decreases with temperature and is zero at the critical point. If the value
of the enthalpy of vapourisation is know at one point, the method of Watson can be used to describe
the enthalpy of vapourisation at any other temperature:
Watson
0.38
1 Tr,1
h vap,2 = h vap,1 (41)
1 T
r,2
Example: Estimate the enthalpy of vapourisation for ethyl acetate at 450.0 K using the normal boiling
point as reference and using the method of Watson
Perry
C 2 + C3 Tr + C 4 (Tr )2
h f = C1 (1 Tr ) (42)
Where C1 through C4 are component specific parameters, listed in table 2-193 page 2-156 to 2-160
th
(7 Edition)
Example: Estimate the enthalpy of vapourisation for ethyl acetate at 450 K using the method of Perry
The enthalpy of fusion hfus is defined as the difference of the enthalpies of a unit mole or mass of a
solid and liquid at its melting temperature and one atmosphere of pressure. Basically, the enthalpy of
fusion is the amount of energy required to melt a solid at its melting temperature and one atmosphere
of pressure. Similarly, the enthalpy of fusion is the amount of energy released when a liquid solidifies
at its melting temperature and one atmosphere of pressure. Perry list the enthalpy of fusion for a
number of compounds.
Correlations regarding the enthalpy of fusion are not as accurate as those for the enthalpy of
vapourisation and generally rely on group contribution methods. These group contribution methods
are complicated and beyond the scope of this course. (For additional reading see page 2-250 and the
th
tables on pages 2-252 and 2-253 in Perry, 7 Edition).
The enthalpy of formation is the energy required to form the compound at a specific temperature
(usually at 298 K) from its elements. The enthalpy of formation is often used in chemical reaction
thermodynamics, hence its importance here. The enthalpy of formation of a number of compounds is
listed in sources such as Physical Chemistry Textbooks and in Properties of Gases and Liquids by
Reid and Prausnitz. However, on occasion the values are not available and need to be estimated.
Constantinou and Gani proposed a group contribution method to calculate the enthalpy of formation at
298 K:
The heat of formation can also be estimated from the heats of combustion (if available). This method
is quite useful, especially for organic compounds containing N, S, O etc.
Example: Estimate the heat of formation for liquid ethanol using heat of combustion of ethanol
Similarly, Hesss Law together with information on other chemical reactions can be used to determine
the heat of formation. This was discussed in Engineering Chemistry 123.
5 PHYSICAL PROPERTIES
Most of the properties discussed above concern themselves with the thermodynamic and critical
properties of substances. These are the properties most commonly used in thermodynamics.
Substances do, however, also have a number of physical properties which are important in
engineering calculations, for example viscosity, thermal conductivity, diffusivity and surface tension.
The amount of data available regarding these properties varies and often, in the absence of reliable
experimental data, these properties need to be estimated. Estimation of these properties is beyond the
scope of this course yet similar methods as those used for the above discussed properties are used.
For further information consult sources such as Perrys Chemical Engineers Handbook and Properties
of Gases and Liquids.
6 WEB SOURCES
With the coming of the electronic age, a large amount of data is available electronically. However, due
to the abundance of data and ease of publication, one needs to exercise caution with unknown
sources. The American National Institute of Standards and Technology (NIST) has a website with very
reliable data. Thermodynamic and physical data for a number of pure components is available with
http://webbook.nist.gov/chemistry/fluid/
7 NOMENCLATURE
Superscripts
ig Refers to the property of an ideal gas
sat Refers to the property at saturated conditions
Subscripts
1 Refers to the property at condition 1
2 Refers to the property at condition 2
298K Refers to the property at 298 K
b Refers to the property at the normal boiling point
bi Refers to the contribution of the group i to the normal boiling point
(Constantinou and Gani method)
c Refers to the property at the critical point
8 REFERENCES
The following general references are good sources of physical properties and their estimation:
th
[1] Perry, R.H.; Green, D.W. (Ed) (1997) Perrys Chemical Engineering Handbook, 7 Edition
(International Edition), McGraw-Hill
th
[2] Reid, R.C.; Prausnitz, J.M.; Poling, B.E. (1987) Properties of Gases and Liquids, 4 Edition,
McGraw-Hill
th
[3] Lide, D.R. (Ed.) (1997) CRC Handbook of Chemistry and Physics, 77 Edition, CRC Press
Other References
[1] Constantinou, L.; Gani, R. (1994) New Group Contribution Method for Estimating Properties of
Pure Compounds, AIChE Journal 40 (10) 1697 1710.
[2] Rika, V.Jr.; Domalski, E.S.(1993) Estimation of the Heat Capacities of Organic Liquids as a
Function of Temperature Using Group Additivity. I. Hydrocarbon Compounds, Journal of
Physical and Chemical Reference Data 22 (3) 597 618.
[3] Rika, V.Jr.; Domalski, E.S.(1993) Estimation of the Heat Capacities of Organic Liquids as a
Function of Temperature Using Group Additivity. I. Compounds of Carbon, Hydrogen,
Halogens, Nitrogen, Oxygen, and Sulphur, Journal of Physical and Chemical Reference Data
22 (3) 619 655.
Table 1: Group contribution paramters for the Lydersen method to calculate Tc and Pc
(From Perrys Chemical Engineers Handbook, page 2-343, Table 2-385)
Table 2: First order group contribution parameters for the estimation of critical properties and
normal boiling points for the method of Constantinou and Gani
(From AIChE Journal, volume 40, no 10, 1994, pages 1699 and 1700, Table 1)
Table 3: First order group contribution parameters for the estimation of thermodynamic
properties and normal boiling points for the method of Constantinou and Gani
(From AIChE Journal, volume 40, no 10, 1994, page 1700, Table 2)
Table 5: Constants for the Antoine equation to estimate the vapour pressure of some
compounds
th
(From Basic Principles and Calculations in Chemical Engineering, 6 Edition, page 669, Table G1)
NOTE: P in mmHg and T in K
Table 6: Parameters for the method of Harrison and Seaton to calculate ideal gas heat capacity
(From Perrys Chemical Engineerss Handbook, page 2-348, Table 2-387)
Table 8: Group contribution parameters for aromatic hydrocarbon groups for estimation of
vapour heat capacities according to the method of Rihani and Doraiswamy
(From Industrial and Engineering Chemistry Fundamentals, volume 4 no 1, 1965, page 18, Table 2)
Table 10: Group contribution parameters for oxygen containing groups for estimation of
vapour heat capacities according to the method of Rihani and Doraiswamy
(From Industrial and Engineering Chemistry Fundamentals, volume 4 no 1 page 1965, Table 4)
Table 11: Group contribution parameters for nitrogen containing groups for estimation of
vapour heat capacities according to the method of Rihani and Doraiswamy
(From Industrial and Engineering Chemistry Fundamentals, volume 4 no 1, 1965, page 19, Table 5)
o
Table 13: Group contribution parameters for estimation of liquid heat capacity at 25 C
according to the method of Shaw
(From Journal of Chemical and Engineering Data, volume 14 no 4, page 464, Table 2)
Table 14: Group contribution parameters for linear hydrocarbon groups for estimation of liquid
heat capacities according to the method of Rika and Domalski
(From Journal of Physical and Chemical Reference Data, volume 22 no 3, page 604, Table 5)